4- methylbenzene-, sodium complex with

Monolayered cyclophane complexes of type 263 are also reduced by sodium bis(methoxyethoxy)aluminum hydride (Red-Al) to give (i74-diene)-(i76-cyclophane)ruthenium(0) complexes (Scheme 33). If the benzene ring of 263 (arene = benzene) is converted to the (1,3-cyclohexadiene)-ruthenium(O) derivative 271, however, when the corresponding rj6-hexa-methylbenzene is reduced with Red-Al, the product is the (if-1, 4-cyclohexadiene)ruthenium(0) complex 288. Synthesis of 271 can... 

These methods are now easy to apply. 4-Methylbenzene-1,2-dithiol is a commercial product and benzene-1,2-dithiol is conveniently prepared by reacting anthranilic acid with isopentyl nitrite in the presence of carbon disulfide. 2-Isopentyloxy-l,3-benzodithiole thus obtained, treated by the tetrafluoroboric/ether complex gives, in 65-70% yield, 1,3-benzo-dithiolium tetrafluoroborate, which is easily cleaved by sodium in liquid ammonia, giving benzene-1,2-dithiol in 80-85% yield (Scheme 11) ... 

A solution of 4-[(2 )-(2-acetoxypropyl)]-5-amino-l,2-dimethoxy-3-methylbenzene (1.96 g, 7.33 mmol) and tricarbonyl(ri -cyclohexadienylium)iron tetrafluoroborate (1.12 g, 3.66 mmol) in acetonitrile (30 mL) was stirred at room temperature for 9 days in air. A saturated aqueous solution of sodium hydrogen carbonate (20 mL) was added to the reaction mixture and the aqueous layer was extracted with ethyl acetate (3 x 20 mL). The combined organic layers were washed with water (2 x 20 mL) and dried with sodium sulfate. After removal of the solvent, the residue was subjected to flash chromatography (hexane/ethyl acetate/triethylamine, 8 2 1) on silica gel to afford the tricarbonyl(il -4a,9a-dihydrocarbazole)iron complex as a bright yellow viscous liquid [a]n = -13.0 (c = 0.5, CHCI3) 1.67g(94%). ... 

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